Polyelectrolyte multilayer thin films [poly(diallyl dimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA)] for the synthesis of CuS and ZnS nanoparticles were prepared. The CuS/ ZnS nanoparticles in situ synthesised by immersing the PDDA/PAA polyelectrolyte multilayer thin films into Cu2+ (or Zn2+) and Na2S aqueous solutions alternately, which were characterised in detail by UV visible absorption spectroscopy, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) analysis. The CuS and ZnS nanoparticles doped polyelectrolyte multilayer thin films were synthesised by the layer-by-layer molecular deposition technology and in situ synthesis method. The coefficient of friction (COF) decreased with the in situ synthesis CuS and ZnS nanoparticles doped into the polyelectrolyte layers. The in situ nanoparticles exhibited enhanced wear resistance performance of the plain polyelectrolyte multilayers.